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Title: Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Abstract

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Inventors:
;
Issue Date:
Research Org.:
Wisconsin Alumni Research Foundation, Madison, WI (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1423443
Patent Number(s):
9903028
Application Number:
15/167,053
Assignee:
WISCONSIN ALUMNI RESEARCH FOUNDATION (Madison, WI)
Patent Classifications (CPCs):
C - CHEMISTRY C08 - ORGANIC MACROMOLECULAR COMPOUNDS C08H - DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
DOE Contract Number:  
FC02-07ER64494
Resource Type:
Patent
Resource Relation:
Patent File Date: 2016 May 27
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stahl, Shannon S., and Rafiee, Mohammad. Nitroxyl-mediated oxidation of lignin and polycarboxylated products. United States: N. p., 2018. Web.
Stahl, Shannon S., & Rafiee, Mohammad. Nitroxyl-mediated oxidation of lignin and polycarboxylated products. United States.
Stahl, Shannon S., and Rafiee, Mohammad. Tue . "Nitroxyl-mediated oxidation of lignin and polycarboxylated products". United States. https://www.osti.gov/servlets/purl/1423443.
@article{osti_1423443,
title = {Nitroxyl-mediated oxidation of lignin and polycarboxylated products},
author = {Stahl, Shannon S. and Rafiee, Mohammad},
abstractNote = {Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {2}
}

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